Wafer storing system having vessel coated with ozone-proof material and method of storing semiconductor wafer

ABSTRACT

A gate oxide layer grown on a semiconductor wafer is liable to be contaminated by organic compound particles in a clean room between the growth of the oxide and the next deposition step, and the semiconductor wafer is sealed in ozonic ambience in a vessel coated with an inner wall of ozone-proof material such as chromium oxide so that the ozone decomposes the organic compound particles without producing new particles.

This application is a division of Ser. No. 08/883,831, filed Jun. 27,1997, now U.S. Pat. No. 5,944,193.

FIELD OF THE INVENTION

This invention relates to a semiconductor wafer storing technology and,more particularly, to a wafer storing system having a vessel coated withozone-proof material and a method of storing a semiconductor wafer.

DESCRIPTION OF THE RELATED ART

A field effect transistor is an important circuit component used in asemiconductor integrated circuit device, and a large number of fieldeffect transistors are fabricated on a semiconductor wafer. When thefield effect transistor is fabricated on the semiconductor wafer, a thingate oxide layer is grown on active areas in the major surface through athermal oxidation, and conductive material such as polysilicon isdeposited over the thin gate oxide layer. The conductive layer ispatterned into gate electrodes by using a photo-lithography and anetching, and dopant impurity is ion implanted into the active areas in aself-aligned manner with the gate electrodes.

Thus, the semiconductor wafer is firstly placed into a thermal oxidizingapparatus, and, thereafter, is moved from the thermal oxidizingapparatus to a reaction chamber of a deposition system. While thesemiconductor wafer is being conveyed from the thermal oxidizingapparatus to the reaction chamber of the deposition system, there is apossibility that the thin gate oxide layer is contaminated. Although thethermally oxidizing apparatus and the deposition system are installed ina clean room, contaminant is not perfectly avoidable, and thesemiconductor wafer is exposed to the contaminant.

Dust particles of metal and organic compound are typical examples of thecontaminant. If the gate oxide layer is contaminated by the metalparticles and the organic compound particles, the conductive material isdeposited over the contaminated gate oxide layer, and is left betweenthe gate oxide layer and the gate electrode. The contaminantdeteriorates the electric properties of the gate oxide layer as reportedby Kimura et. al. in “Time Dependent Dielectric Breakdown PhenomenaCaused by Carbon Organic Contaminants”, Proceedings of 1994 AutumnMeeting of Society of Applied Physics, 19p-ZC-4. The paper teaches thatthe time dependent dielectric breakdown is increased due to carbonorganic contaminants absorbed in the natural oxide grown on a siliconlayer.

In order to eliminate the dust, particles from the clean room, a highefficiency particular air filtering system or an ultra low penetrationair filtering system is installed in the clean room. The air filteringsystem decreases the dust particles in the clean room. However, the airfiltering system hardly eliminates organic compound particles from theair, and the gate oxide layer is liable to be contaminated by theorganic compound particles.

Japanese Patent Publication of Unexamined Application No. 5-259445discloses a storing technology for a semiconductor wafer. The JapanesePatent Publication of Unexamined Application proposes to store asemiconductor wafer in vacuum or inert gas such as nitrogen gas.

The prior art storing technology disclosed in the Japanese PatentPublication of Unexamined Application is effective against thecontamination in so far as the semiconductor wafer is placed in thevacuum or the inert gas immediately after the growth of the gate oxidelayer. However, if the semiconductor wafer is exposed to the atmospherein the clean room, the time dependent dielectric breakdown still takesplace at a high percentage.

SUMMARY OF THE INVENTION

It is therefore an important object of the present invention to providea wafer storing technology which is effective against the contaminationby the organic compound particles.

The present inventor contemplated the problem inherent in the prior artwafer storing technologies, and noticed that the prior art wafer storingambience merely sealed a semiconductor wafer in dust-free atmosphere. Ifa wafer storing ambience attacked the organic compound particles, thewafer storing ambience would clean the semiconductor wafer bydecomposing the organic compound. The present inventor stored asemiconductor wafer in ozone, and evaluated the cleaning capability ofozone as follows.

The present inventor prepared samples where silicon oxide had been grownto 80 angstroms on semiconductor wafers. Conductive material wasdeposited over the silicon oxide layer of the first sample group withinan hour after the growth. The second sample group was stored in a cleanroom for a week, and, thereafter, the conductive material was depositedover the silicon oxide layer. The third sample group was stored in thenitrogen ambience for a week, and, thereafter, the conductive materialwas deposited over the silicon oxide layer. The fourth sample group wasstored in ozone sealed in a vessel formed of teflon orpolytetrafluoroethylene for a week, and, thereafter, the conductivematerial was deposited over the silicon oxide layer.

The present inventor evaluated the data storing technologies for thefirst to fourth sample groups from the aspect of the time dependentdielectric breakdown. The present inventor applied potential across thesilicon oxide layers of the first to fourth sample groups, andinvestigated the cumulative percent defective of each sample group interms of the breakdown charge. The potential was applied to 1 squaremillimeter, and the injection current density was 0.1 ampere/cm².

The cumulative percentage defective of each group was plotted in FIG. 1.Plots PL1, PL2, PL3 and PL4 represented the first sample group, thesecond sample group, the third sample group and the fourth sample group,respectively. The wafer storing technology in ozone did not drasticallyimprove the cumulative percent defective.

The present inventor investigated why the ozone did not improve thecumulative percent defective. The present inventor found that ozone haddecomposed the teflon. Although ozone decomposed the organic compoundparticles adhered to the semiconductor wafer before the entry into theteflon vessel, the teflon newly supplied organic compound particles tothe semiconductor wafer, and the semiconductor wafer was contaminated,again.

Although a quartz vessel disclosed in Japanese Patent Publication ofUnexamined Application No. 60-32315 or 61-39524 was effective againstozone, it was difficult to form a quartz vessel large enough to store aplurality of semiconductor wafers without a special facility. Moreover,the quartz was so heavy that operators suffered from an inability toeasily manipulate the vessel.

To accomplish the object, the present invention proposes to coat asealing vessel with material hardly decomposed by ozone.

In accordance with one aspect of the present invention, there isprovided a wafer storing system for storing at least one semiconductorwafer comprising: a vessel having an inner wall formed of ozone-proofmaterial and defining an airtight chamber so as to accommodate the atleast one semiconductor wafer; and a source of ozone supplying ozone tothe airtight chamber.

In accordance with another aspect of the present invention, there isprovided a method of storing at least one semiconductor wafer,comprising the steps of: a) preparing a vessel having an inner wallformed of ozone-proof material and defining an airtight chamber; b)placing at least one semiconductor wafer in the airtight chamber; c)sealing the at least one semiconductor wafer in the airtight chamber;and d) creating ozonic atmosphere in the airtight chamber.

BRIEF DESCRIPTION OF THE DRAWINGS

The features and advantages of the wafer storing system and the methodaccording to the present invention will be more clearly understood fromthe following description taken in conjunction with the accompanyingdrawings in which:

FIG. 1 is a graph showing the cumulative percent defective in terms ofbreakdown charge investigated for the different wafer storingtechnologies;

FIG. 2 is a cross sectional view showing the structure of a waverstoring system according to the present invention;

FIG. 3 is a side view showing the wafer storing system; and

FIG. 4 is a graph showing a cumulative percent defective in terms ofbreakdown charge achieved by the wafer storing system according to thepresent invention.

DESCRIPTION OF THE PREFERRED EMBODIMENT

Referring to FIGS. 2 and 3 of the drawings, a wafer storing systemembodying the present invention largely comprises a wafer storing vessel1 and a gas supplying sub-system 2 connected to the wafer storing vessel1. The wafer storing vessel 1 includes a stationary case 1 a and aslidable lid 1 b, and the stationary case 1 a and the slidable lid 1 bdefines an airtight chamber 1 c when the slidable lid 1 b is closed.

The stationary case 1 a has an outer wall 1 d formed of synthetic resinsuch as, for example, polytetrafluoroethylene and an inner wall 1 e ofozone-proof material laminated on the outer wall 1 d. The stationarycase 1 a further has a pedestal portion 1 f, and two cylindrical holes 1g/1 h are formed in the pedestal portion 1 f.

The slidable lid 1 b also has an outer wall 1 i formed of the syntheticresin and an inner wall 1 j formed of the ozone-proof material. In thisinstance, the ozone-proof material is chromium oxide. The slidable lid 1b further has a pair of guide rods 1 k inserted into the cylindricalholes 1 g/1 h, and the guide rods 1 k are slidable into and out of thepedestal portion 1 f along the cylindrical holes 1 g/1 h.

A quartz boat 1 m is attached to the slidable lid 1 b, and a pluralityof slits 1 n are formed in the quartz boat 1 m. A plurality ofsemiconductor wafers 3 are inserted into the slits 1 n so as to stand onthe quartz boat 1 m. When the slidable lid 1 b is drawn from thestationary case 1 a, the quartz boat 1 m is exposed to an operator, andthe operator places the semiconductor wafers 3 onto and picks them upfrom the quartz boat 1 m. On the other hand, when the slidable lid 1 bis pushed into the stationary case 1 a, the slidable lid 1 b is broughtinto contact with the stationary case 1 a, and the semiconductor wafers3 are sealed in the airtight chamber 1 c.

The quartz boat 1 m is spaced from the inner wall 1 d of the stationarycase 1 a by distance c, and never scratches the inner wall 1 d.

The gas supplying sub-system 2 includes an ozone generator 2 a, an inletpipe 2 b connected between the ozone generator 2 a and the airtightchamber 1 c, an exhaust fan 2 c, an outlet pipe 2 d connected betweenthe airtight chamber 1 c and the exhaust fan 2 c and a nitrogen source 2e connected to the inlet pipe 2 b. Ozone and nitrogen are selectivelysupplied to the airtight chamber 1 c through the inlet pipe 2 b. Theozone is upwardly blown into the airtight chamber 1 c, and is evacuatedfrom the airtight chamber 1 c by the exhaust fan 2 c. The ozonecirculates around the semiconductor wafers 3, and decomposes organiccompound particles. However, the inner walls 1 e/1 j withstands theozone.

When the airtight chamber 1 c is designed to accommodate twenty-fivesemiconductor wafers 3, the volume of the airtight chamber 1 c is about800 cubic centimeters, and the gas supplying sub-system 2 supplies ozoneat 500 sccm so as to perfectly create the ozonic ambience in the airtight chamber 1 c within 30 minutes.

The present inventor investigated various kinds of material proofagainst ozone, and concluded that the chromium oxide was the mostappropriate ozone-proof material, presently. However, any ozone-proofmaterial is available for the inner walls 1 e/1 j in so far as itproduces organic compound particles less than the teflon.

The semiconductor wafers 3 are stored in the wafer storing system shownin FIGS. 2 and 3 as follows. Field effect transistors are assumed to befabricated on the semiconductor wafers 3 through the process sequencedescribed hereinbefore.

When silicon oxide is grown on the active areas defined in thesemiconductor wafers 3, an operator inserts the semiconductor wafers 3into the slits of the quartz boat 1 m, and the semiconductor wafers 3stand on the quartz boat 1 m. The operator pushes the slidable lid 1 binto the stationary case 1 a, and the semiconductor wafers 3 are sealedin the airtight chamber 1 c.

The ozone generator 2 a supplies ozone into the airtight chamber 1 c,and the exhaust fan 2 c evacuates the air and the ozone from theairtight chamber 1 c. As described hereinbefore, the ozone supplyingsub-system 2 supplies the ozone at 500 sccm, and perfectly replaces theair in the chamber 1 c of 8000 cubic centimeters with the ozone within30 minutes.

When the ozonic ambience is created in the airtight chamber 1 c, theflow rate of ozone is decreased to 10 sccm until a deposition system(not shown) is ready for start. When the deposition system is ready forstart, the nitrogen source 2 e supplies the nitrogen into the airtightchamber 1 c, and the ozone is replaced with the nitrogen. When the ozoneis replaced with the nitrogen, the slidable lid 1 b is drawn from thestationary case 1 a, and the semiconductor wafers 3 are taken out fromthe quartz boat 1 m. The ozone has been already replaced with thenitrogen, and the ozone is not diffused into the clean room. Thesemiconductor wafers 3 are placed in the reaction chamber of thedeposition system, and conductive material is deposited over the siliconoxide layers.

The present inventor evaluated the wafer storing system according to thepresent invention as follows. The present inventor firstly preparedsamples where silicon oxide had been grown to 80 angstroms on siliconwafers. Conductive material was deposited over the silicon oxide layerof the first sample group within an hour after the growth. The secondsample group was stored in a clean room for a week, and, thereafter, theconductive material was deposited over the silicon oxide layer. Thethird sample group was stored in the wafer storing system according tothe present invention for a week, and, thereafter, the conductivematerial was deposited over the silicon oxide layer.

The present inventor checked the first to third sample groups to seewhether or not the time dependent dielectric breakdown took place. Thepresent inventor applied potential across the silicon oxide layers ofthe first to third sample groups, and investigated the cumulativepercent defective of each sample group in terms of the breakdown charge.The potential was applied to 1 square millimeter, and the injectioncurrent density was 0.1 ampere/cm².

The cumulative percentage defective of each group was plotted in FIG. 4.Plots PL5, PL6 and PL7 represented the first sample group, the secondsample group and the third sample group, respectively. As will beunderstood from plots PL5 to PL7, the inner walls 1 e/1 j effectivelyprevented the outer walls 1 d/1 i from exposure to the ozone, and thewafer storing system according to the present invention improved thetime dependent dielectric breakdown characteristics of the third samplegroup to the same level as the samples covered with the conductivematerial without an hour delay.

As will be appreciated from the foregoing description, the ozonedecomposes organic compound particles adhered to the semiconductorwafers 3 during the exposure to the air in the clean room, and the innerwalls 1 e/1 j of the ozone-proof material do not produce organiccompound particles during the storage of the semiconductor wafers 3 inthe ozonic ambience. For this reason, the wafer storing system accordingto the present invention keeps the silicon oxide layers on thesemiconductor wafer clean, and the clean silicon oxide layers improvethe time dependent dielectric breakdown characteristics of field effecttransistors.

Moreover, the laminated structure of the inner/outer walls 1 d/1 e/1 i/1j is lighter than a quartz vessel, and the outer walls 1 d/1 i of thesynthetic resin withstands an unavoidable impact. This results in goodmanipulability of the wafer storing vessel 1.

Although particular embodiments of the present invention have been shownand described, it will be obvious to those skilled in the art thatvarious changes and modifications may be made without departing from thespirit and scope of the present invention.

For example, the boat 1 m may be separated from the slidable lid 1 m sothat an operator manually inserts the boat 1 m into and takes out itfrom the airtight chamber 1 c.

The outer walls 1 d/1 i may be formed of perfluoroalkoxi,polyvinylchloride, tetrafluoroethylene, copolymer betweentetrafluoroethylene and hexafluoropropylene, copolymer betweentetrafluoroethylene and ethylene, polychlorotrifluoroethylene,polyvinylidenfluoride and vinylidenfluoride.

What is claimed is:
 1. A method of processing at least one semiconductorwafer, comprising the steps: (a) forming an oxide layer on a surface ofsaid at least one semiconductor wafer; (b) providing a vessel having aninner wall formed of ozone-proof material and defining an air-tightchamber; (c) placing said at least one semiconductor wafer with saidoxide layer in said air-tight chamber; (d) sealing said at least onesemiconductor wafer with said oxide layer in said air-tight chamber; (e)creating an ozonic atmosphere in said air-tight chamber; (f) maintainingsaid at least one semiconductor wafer with said oxide layer in saidozonated atmosphere in said chamber for a selected time period; (g)terminating containment of said wafer in said ozonic atmosphere aftersaid time period; and (h) depositing a conductive layer on said oxidelayer on said at least one semiconductor wafer.
 2. A method as in claim1, wherein a field-effect transistor is produced on said wafer surface,said oxide layer and said conductive layer together being formed toprovide a gate for said transistor.
 3. The method as set forth in claim1, in which said ozone-proof material is chromium oxide.
 4. The methodas set forth in claim 1, in which said vessel has a multi-layeredstructure having said inner wall.
 5. The method as set forth in claim 4,in which said inner wall is laminated on an outer wall formed ofsynthetic resin.
 6. The method as set forth in claim 5, in which saidinner wall is formed of chromium oxide, and said outer wall is formed ofthe synthetic resin selected from the group consisting ofpolytetrafluoroethylene, perfluoroalkoxi, polyvinylchloride,tetrafluoroethylene, copolymer between tetrafluoroethylene andhexafluoropropylene, copolymer between tetrafluoroethylene and ethylene,polychlorotrifluoroethylene, polyvinylidenfluoride andvinylidenfluoride.
 7. The method as set forth in claim 1, furthercomprising the step of replacing said ozonic atmosphere with an inertatmosphere in step (g).
 8. The method as set forth in claim 7, in whichsaid inert atmosphere is created by nitrogen.